Anion binding in water drives structural adaptation in an azaphosphatrane-functionalized FeII4L4 tetrahedron

Dawei Zhang; Tanya K. Ronson; Jesús Mosquera; Alexandre Martinez; Laure Guy; Jonathan R. Nitschke

doi:10.1021/jacs.7b02950

Anion binding in water drives structural adaptation in an azaphosphatrane-functionalized Fe^II₄L₄ tetrahedron

Dawei Zhang, Tanya K. Ronson, Jesús Mosquera, Alexandre Martinez^*, Laure Guy, Jonathan R. Nitschke

^*Corresponding author for this work

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

86 Citations (Scopus)

19 Downloads (Pure)

Abstract

Anion-templated aqueous self-assembly resulted in the formation of an endohedrally functionalized Fe^II₄L₄ tetrahedron from azaphosphatrane-based subcomponents. This new water-soluble cage is flexible and able to encapsulate anions with volumes ranging from 35 to 219 Å³ via hydrogen bonding and electrostatic interactions. It structurally adapts in response to the size and shape of the template anions, dynamically adopting a conformation either where all four azaphosphatrane ⁺P-H vectors point inward, or else where one points outward and the other three inward. The two cage isomers can coexist in solution and interconvert. A shape memory phenomenon was observed during guest displacement because guest exchange occurs more rapidly than structural reconfiguration.

Original language	English
Pages (from-to)	6574-6577
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	19
Early online date	8 May 2017
DOIs	https://doi.org/10.1021/jacs.7b02950
Publication status	Published - 17 May 2017

Funding

This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC EP/M008258/1). The authors thank the Department of Chemistry NMR facility, University of Cambridge for performing someNMRexperiments, and the EPSRC UK National Mass Spectrometry Facility at Swansea University for carrying out high-resolution mass spectrometry. D.Z. acknowledges a grant from the China Scholarship Council, Accueil Doc Bursary from France Rhone-Alpes Region, and Enveloppe AttractiviteFellowship from ENSLyon for Ph.D. studies.

Keywords

anion binding
water-soluble cage
azaphosphatrane

Access to Document

10.1021/jacs.7b02950Licence: CC BY 4.0

Zhang-etal-JACS-2017-Anion-binding-in-water-drives-structural-adaptationFinal published version, 1.58 MBLicence: CC BY 4.0

Cite this

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abstract = "Anion-templated aqueous self-assembly resulted in the formation of an endohedrally functionalized FeII4L4 tetrahedron from azaphosphatrane-based subcomponents. This new water-soluble cage is flexible and able to encapsulate anions with volumes ranging from 35 to 219 {\AA}3 via hydrogen bonding and electrostatic interactions. It structurally adapts in response to the size and shape of the template anions, dynamically adopting a conformation either where all four azaphosphatrane +P-H vectors point inward, or else where one points outward and the other three inward. The two cage isomers can coexist in solution and interconvert. A shape memory phenomenon was observed during guest displacement because guest exchange occurs more rapidly than structural reconfiguration.",

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AU - Guy, Laure

AU - Nitschke, Jonathan R.

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AB - Anion-templated aqueous self-assembly resulted in the formation of an endohedrally functionalized FeII4L4 tetrahedron from azaphosphatrane-based subcomponents. This new water-soluble cage is flexible and able to encapsulate anions with volumes ranging from 35 to 219 Å3 via hydrogen bonding and electrostatic interactions. It structurally adapts in response to the size and shape of the template anions, dynamically adopting a conformation either where all four azaphosphatrane +P-H vectors point inward, or else where one points outward and the other three inward. The two cage isomers can coexist in solution and interconvert. A shape memory phenomenon was observed during guest displacement because guest exchange occurs more rapidly than structural reconfiguration.

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